Monoazo dyestuffs of low solubility in water



United States Patent 3,150,516 MONOAZO DYESTUFFS 0]? LOW SOLUBILHTY IN WATER Ernest Merian, Bottmingen, Otto Senn, Arlesheim, and Walter Wehrli, Riehen, Switzerland, assignors to Sandoz A.G., Basel, Switzerland No Drawing. Filed Feb. 5, 1959, Ser. No. 791,277 Claims priority, application Switzerland Feb. 7, 1958 4 Claims. (Cl. 260205) This invention relates to new monoazo dyestuffs which have low solubility in water and are of the general formula CHz-Ri CHz-R2 R4 R Y wherein R stands for hydrogen, low molecular alkyl, low molecular hydroxyalkyl, low molecular alkoxy alkyl, low molecular acetoxyalkyl, low molecular propionyloxyalkyl, or a radical of a carbamic acid alkyl ester,

R for low molecular acetoxyalkyl, low molecular propionyloxyalkyl, low molecular cyanoalkyl or a radical of a carbamic acid alkyl ester,

R for an amino group which may be monoor disubstituted,

R for hydrogen, halogen, methyl, ethyl, trifluoromethyl,

i methoxy, ethoxy, or together with R for a -CH=CH CH CH- chain,

R for hydrogen, halogen, cyano, trifluoromethyl, low molecular alkylsulfonyl, a sulfonic acid amide group which may be monoor disubstituted, or together with R, a --CH=OHCH=CH- chain,

R for hydrogen or halogen, and a Y for hydrogen, halogen, a low molecular alkyl or alkoxy radical, the trifiuoromethyl or trifluoroacetylamino radical, or an alkanoylamino radical with not more than 18 carbon atoms.

The process for the production of the new monoazo dyestuffs of low water-solubility consists in combining 1 mol of the diazo compound of an amine of the general formula it, 7 its (II) wherein R R R and R possess the aforecited meanings, with 1 mol of a compound of the formula I CHiR2 Y (III) wherein R R and Y possess the aforecited meanings.

The diazo compounds are coupled with the coupling components in an acid medium, which may be buffered.

A number of the new monoazo dyestuifs dye from aqueous suspension polyamide fibers (e.g. nylon, Perlon, registered trademark), cellulose ester fibers (eg. secondary cellulose acetate, cellulose triacetate), polyvinyl fibers, polyacrylonitrile fibers and polyester fibers (e.g. Dacron, Terylene, registered trademarks) in brilliant yellow, orange and scarlet shades. The dye ings obtained with them possess very good fastness to light, gas fumes, washing, perspiration, water and sea 3,050,516 Patented Aug. 21, 1962 water, and are white dischargeable. Viscose rayon, cotton and wool are comparatively well reserved by the dyestufis, especially when the goods are aftertreated with hydrosulfites. With those dyestuffs of the present invention which possess sufficient afiinity for cellulose triacetate and polyester fibers it is possible for the first time to produce on these fibers bright orange shades which are fast to light, pleating, sublimation, and heat setting. The solution ofthis technical problem was important above all in connection with brown mixtures. Certain of the new monoazo dyestuffs are also suitable for coloring oils, lacquers and synthetic resins, and for the dyeing of artificial fibers in the mass.

The spun-dyed shades given by these dyestuffs in secondary cellulose acetate and cellulose triacetate have high fastness to light, washing, perspiration, gas fumes, cross dyeing, alkaline bleaching, oxalic acid, dry cleaning, and peroxide bleaching. Also, they show excellent fastness to Water, sea water, soap baths, crocking, decatizing, and pressing.

A great number of the amines which are employed here in the form of their diazo compounds are new. They are produced by the normal methods by the reaction of compounds of the formula ings, with ammonia at high temperatures when X stands for fluoro, chloro, bromo or alkoxy, and by treatment of the compounds of Formula IV with hydrolysing agents when X stands for an acylamino group.

A further process for the production of the primary amines, some of which are new, consists in reacting 1 mol of a compound of the formula I R4 R5 (V) wherein R and R and R possess the aforenamed meanings and Z represents halogen, with ammonia, or with a primary or secondary amine. This process of acid amide formation is carried out preferably in presence of an acid-binding agent or with the aid of an excess of the amine or ammonia which forms one of the reactants. R .and/or R halogen may also be introduced by direct halogenative processes of l-aminobenzene-4-sulfamides. The new products are isolated by one of the common basic operations, e.g. filtration, evaporation of the solvent, salting out, precipitation from the solvent with a suitable agent etc., where necessary after neutralization of the hydrolysing solution.

The new intermediate products are also intended for use in the production of pharmaceutical preparations.

In the following examples the parts and percentages are by weight and the temperatures in degrees centigrade.

dropwise addition of an aqueous solution of 7 parts of sodium nitrite. To the. resultant diazo solution is added a solution of 20.4 parts of 1-(N-cyanoethyl-N-hydroxyethyl)-amino-3-methylbenzene in 50 parts of water, 50

CHz-CHz- O H is subsequently filtered off, washed free of acid, and dried. It dissolves in organic solvents with an orange coloration and in concentrated sulfuric acid with a red-violet coloration. Applied from aqueous dispersion, it dyes cellulose acetate and nylon in bright, level orange shades. The dyeings have good fastness to light, gas fumes, perspiration, sea water, sublimation, and pleating, and are readily dischargeable.

The corresponding dyestuif (Example 2) obtained from N-cyanoethyl-N-hydroxyethylaminobenzene also dissolves in concentrated sulfuric acid to give red-violet solutions, and the dyeings produced with it on cellulose acetate and nylon possess similar fastness properties. On polyester fibers, however, it has a slightly more yellowish shade.

Example 3: 287 parts of l-acetylaminonaphthalene-4- sulfonic acid are added to 833 parts of chlorosulfonic acid at 1020. The solution is stirred for 2 hours at 20 and then heated to 50. After 16 hours at this temperature the reaction mass is run into a mixture of 8000 parts of ice and 1000 parts of water, upon which 1-acetylaminonaphthalene-4-sulfonic acid chloride precipitates. This is isolated by filtration and Washed free of acid. The moist press cake obtained is mixed at room temperature with 500 parts of Water, 500 parts of ice and 100 parts of methylamine. After 16 hours the temperature is gradually increased to 50. Stirring is continued for 16 hours at the same temperature and after this time the precipitated l-acetylaminonaphthalenelsulfonic acid methylamide, which melts at 221-225" in the crude state, is filtered off, washed free of alkali, and dried. 27.8 parts of the acetyl compound so formed are added to 200 parts of Water and 32 parts of concentrated hydrochloric acid and saponified by boiling for 6 hours. The new intermediate product obtained in hydrochloric acid solution has the formula It is diazotized as described in Example 1 and the diazo compound is added to N-hydroxyethyl-N-cyanoethylrnino benzene. The new dyestuif formed dissolves in organic solvents and in 1% sodium hydroxide with an orange coloration, and in concentrated sulfuric acid with a redviolet coloration.

It is applied to cellulose acetate fibers and polyamide fibers from aqueous suspension at high temperature, preferably in presence of compounds with dispersing action, to give brilliant yellow-orange shades which show good fastness to light, gas fumes, sublimation, and wet treatments. The dyeings are readily dischargeable.

When in place of N-hydroxyethyl-N-cyanoethylaminobenzene aliquot amounts of N-ethylN-cyanoethylaminobenzene (Example 4) or 1-(N-hydroxyethyl-N-cyanoethyl)-amino-3-methyl-benzene (Example 5) are employ- .ed, similar dyestuffs are obtained which exhibit virtually the same light fastness.

On the other hand, by using as coupling components the ethylcarbamic ester of l-(N-ethyl-N-hydroxyethylamino-3-methylbenzene (Example 6), 1-N,N-di-(-acetoxyethyl)-amino-3-acetylaminobenzene (Example 7), l-N, N di (acetoxyethyl) amino-3-acetylaminor6-methoxybenzene (Example 8) or l-N,N-di-(ace-toxyethyl)-amino- 3-propionylaminobenzene (Example 9), dyestuffs of a somewhat more reddish shade are obtained which in part show better fastness to washing.

Example 10: When the parts of methylamine in the first paragraph of Example 2 are replaced by parts of dimethyla-mine, the intermediate product obtained is lacetylaminonaphthalene-4-sulfonic acid dimethylamide with a melting point in the crude state at 200204. It can be hydrolysed in a similar manner to give l-aminonaphthalene-4-sulfonic acid dimethylamide of the formula When the diazo compound obtained from this is combined in a similar way with 1-(N-hydroxyethyl-N-cyanoethyl)- amino-3-methylbenzene, an orange disperse dyestuif is obtained which has similar fastness properties and dissolves in concentrated sulfuric acid with a red-violet coloration.

By using in place of the aforementioned diazo compound one from l-aminonaphthalene-4-sulfonic acid-N- methyl-N-phenylamide (Example 11) or l-aminonaphthalene-4-sulfonic acid-N-(Zt-hydroxy) ethyl-N-phenylamide (Example 12) dyestuffs of very good solubility in acetone are obtained which are suitable for the dope dyeing of secondary cellulose acetate and cellulose triacettate.

Example 13: 23.45 parts of l-amino-Z-chlorobenzene- 4-sulfonic acid dimethylamide are aded to 130 parts of concentrated sulfuric acid at 60. In the course of 1 hour 7 parts of solid sodium nitrite are added to the solution. The reaction mass is stirred for 1 hour at 60' and then run into a mixture of 500 parts of ice and 200 parts of water. if a slight excess of nitrous acid is present it is destroyed by an addition of 0.5 part of amidosulfonic acid. To the diazo solution obtained are added 18 parts of N-ethyl-N-cyanoethylaminobenzene (3.1 115). Formation of the dyestuif takes place immediately. The dyestuff paste is filtered off, the residue Washed free of acid, and dried. The new dyestuff corresponds to the formula 01 CH I /C2H5 CH CHz- C H2- 0 N (Melting point -161") It dyes secondary cellulose acetate and cellulose triacetate, polyamide fibers and polyester fibers in brilliant orange shades of high tinctorial strength which have good fastness to light and excellent fastness to washing, perspiration, sea water, gas fumes, sublimation, pleating and cross dyeing. The dyeings are dischargeable with ease and the dyestutf reserves viscose rayon and cotton satisfactorily; the wool reserve too is fairly good and can be improved by suitable aftertreatment, e.g. with hydrosulfite.

A dyebath is prepared with 1 part of the above-described dyestuff dispersed with the aid of Turkey red oil, 6 parts of a sulfonated fatty alcohol and 3000 parts of water. 100 parts of secondary cellulose acetate fabric are entered at room temperature. The temperature of the dyebath is increased to 80 in 1 hour and this temperature maintained for a further hour. After this time the dyeing process is completed. The dyed fabric is removed, rinsed and dried.

Similar dyeing properties are possessed by the following dyestuffs which are produced in an analogous manner:

Example 14: 4-(N-methyl -N -cyanoethyl)-amino-2'- chloroazobenzene-4sulfonic acid amide, MP. l74l75 Example 15: 4-(N-methyl N cyanoethyl)-amino-2- 3,050,516 E chloroazobenzene 4 sulfonic acid methylamide, M.P. Example 40: 4-(N-acetoxyethyl N cyanoethyD-ami- 153-155 110-2.5'-d1ChlOI0aZO b -)31Z6114'-Sl1lf0I11C acid methylamide,

Example 16: 4-(N-methyl N cyanoethyl)-amino-2'- M.P. 160-163". chloroazobenzene-4'-sulfonic acid dimethylamide, M.P. Example 41: 4-(N-rnethyl N cyanoethyD-amino- 148-149. V 5 2'.5'-dichloroazobenzene-4-sulfonic acid-2-hydroxyeth- Example 17: 4-(N-ethyl N cyanoethy1)-amino-2'- ylamide, M.P. 170-171". chloroazobenzene-4-sulfonic acid amide, M.P. 167-169. Example 42: 4-(N-ethyl N cyanoethyl)-amino-2'.5'-

Example 18: 4-(N-ethyl N cyanoethyl)-amino-2- dichloroazobenzenel'-sulfonic acid-2"-hydroxyethylamchlor-oazobenzene-4-sulfonic acid methylarnide, M.P. ide, M.P. 110-112.

136-138". Example 43: 4-(N-propyl N cyanoethyD-amino- Example 19: 4-(N-propyl N cyanoethyl)-amino-2- 2.5'-dichloroazo benzene-4'-sulfonic acid-2"-hyd=roxyethchloroazobenZene-4asulfonic acid amide, M.P. 171-172". ylamide, M.P. 118-l2( Example 20: 4'-(N-propyl N cyanoethyl)-amino-2- The dyestuif 4-(N-ethyl N cyanoet'hyl)-amino-6- chloroazo-benzene-4esulfonic acid methylamide, M.P. chloro-l,1-azobenzene-2.4-di(sulfonic acid methylam- 144-146. ide) (Example 44) with melting point at 170 has a Example 21: 4-(N-butyl N cyanoethyl)arnino-2- somewhat yellower and duller shade, but shows equally chloroazobenzene-4'-sulfonic acid amide, M.P. 145-147. good afiinity for secondary cellulose acetate and gives Example 22: 4(-N-butyl N cyanoethyl)-amino-2- dyeings with good fastness properties. chloroazobenzene-4-sulfonic acid methylamide, M.P. Dyestuffs which are substituted in the 2'-position by 126-129". hydrogen, e.g. Example 45:

Example 23: 4-(N butyl N cy-anoethyl)-amino-2- H g 02m chloroazobenzene-4'-sulfonic acid dimethylamide, M.P. 134-135".

Example 24: 4-(N-acetoxyethyl N cyanoethyl)- H r r ami1'10-2'-h10f0aZ0b6I1Z6I1e-4'-S111f0ni acid amide, P- 25 dye secondary cellulose acetate, cellulose triacetate, poly- 162-164". amide fibers and polyester fibers in fast yellow shades. E p 253 Y Y N y yn- Further dyestuffs possessing similar fastness properties amrho-2'-chloroazobenzene-4-sulfonic acid methylamide, ar

Example 46: 4-(N-acetoxyethyl-N-cyanoethyl)-amino- EXEIDPIB 26? Y Y N Y YU-a i- 3O aZobenzene-4'-sulfonic acid methylamide, M.P. 152-154. no-2-chloroazobenzene-4-sulfonic acid dimethylamide, Example 47: 4-(N-acetoxyethyl-N-cyanoethyl)-amino- M.P. 139-140. azobenzene-4'-sulfonic acid dimethylamide, M.P. 122- Similar dyestuflls are obtained when the sulfonic acid 125. gdirnethylamide group in Example 4 is replace by a Sul- Dyestufis analogous to Example 13 are obtained from ionic acid ethylamide group (Example 27), a sulfonic l-amino-Z-bromobenzene-4-sulfonic acid methyl- (Exacid iso-propylamide (Example 28), a sulfonic acid hyample 48), ethyl- (Example 49), or propylarnide (Examdroxyethylamide group (Example 29) or a sulfonic acid ple 50). Particularly good washing fastness is shown methoxypropyl amide group (Example 30). by the dyestuffs 2'5'dichloroazobenzene-4-sulfonic acid methylamide, and Example 52:

M.P. 202-203. which dye cellulose acetate fibers and polyamide from Example 321 Y N Y Y aqueous dyebaths in red-orange shades. dichloroazobenzene-4-sulfonic acid methylamide, M.P. The dyestuif 4-(N-ethyl-N-cyanoethyl)-amin 2,.t -i 220-222. fluoromethyl-l-l-azobenzene-4-sulfonic acid methylamide Example 331 4-(N-pr0pyl N y-a yn- (Example 53) possesses similar dyeing properties, while 2.5-dichloroazobenzene-4'-sulfonic acid methylamide, the yellower dyestufl 4-(N-acetoxyethyl-N-cyanoethyl) M.P. 136-137. amino-Z-trifluoromethyl-l.1-azobenzene-4-sulfonic acid- EX3II1P1e l -y y N-methyl-phenylamide (Example 54) is more suitable dichloroazobenzene-4'-sulfon1c acid methyl amide, M.P. f the dyeing f fib plastic Sheet d lacquers 3f 157-160 cellulose acetate in the mass.

Example 35: N cyanoethyn'ammo Disperse dyestuffs of redder shade with very good fast- %;gifggi acid amide ness properties are the compounds 4'-(N-acetoxyethyl-N- p 36: y N cyanoethylyanfinoacst cyanoethyl) amino-Z-cyano-l.1-azobenzene-4su1fonic dichloroazobenzene-4-sulfonic acid amide, M.P. 190. acid methylamide (Exflmple 4"(N'methyl' or 'ethyl' Example 37: 4 (N propyl N cyanoethyl) amino N cyanoethyl) am no 2-cyano-1.l-azobenzene-4-sul- 2.5-dichlorozabenzene-4-su1fonic acid amide, M.P. 168- fomc acid methyl amlde (Examples 56+57) and (N-acetoxyethyl)-amino-2'-acetylaminoor -trifluoroacet Example 38: 4-(N-butyl N cyanoethyl)-amino-2'.5- Y 0F -P P y 0-2-cyauo-l,1"-azobenzene-4- dichloroazobenzene 4-sulfonic acid amide, M.P. 156- Sulfonic acid dimethylamide (Examples 5840)- In the following table further monoazo dyestuffs are Example 39; 4-(N-acetoxyethyl N cyangethyn-amirecited which may be produced in an analogous manner no-2.5-dichloroazobenzene4-sulfonic acid amide, M.P. as described in the foregoing examples. They correspond 159-162. to the general Formula I.

Examples 88 and 89: By using in place of the diazo machine and spun to give orange filaments. The dyecompound named in Example 13 one of 1-amino-2.5-diings are characterized by very good fastnessto light, Washchlorobenzene-4-sulfonic acid-N-methyl-N-phenylamide ing, cross dyeing, chlorine, oxalic acid, peroxide, subor 1-arnino-2.5-dichlorobenzene-4-sulfonic acid-N-(2'-hylimation, bleaching, gas fumes and dry cleaning, and are droxy)-ethyl-N-phenylamide, dyestuffs are obtained considerably stable to hydrosulfite. Similar properties which have very good solubility in acetone and are. are possessed by the dyestuff Example 92.

suitable for the dyeing of cellulose acetate fibers in the The latter dyesituff however has a much more yellowish mass. shade in spun-dyed acetate than the above-mentioned dye- Dyeings of particularly good fastness to gas fumes and stuffs.

chlorine are obtained when the dyestuff Example 90: The dyestuffs 4-(N-methylor -ethyl or -acetoxyethy or the dyestulf Example 91: N cyanoethyl) amino 2 cyano 1.1 azobenzeneare dissolved in acetone together with cellulose acetate 4 sulfonic acid N methyl N phenylamideor -N- and the orange-colored mass spun in the normal way by ethyl-N-phenylamide or -N-cyclc-hexylamide (Examples the dry spinning process. 93461), 4 bis (N -acetoxyethyl) amino 2'- The spun dyeing method is as follows: dccanoylamino 2 cyano 1.1 azobenzene 4 sul- 100 parts of secondary cellulose acetate are dissolved fonic acid dimethylamide (Example 102) and the hisin 300 parts of a mixture of solvents consisting of 93% phenylcarbamic acid ester of 4-di-(2"-hydroxy)-ethylof acetone and 7% of methanol. The mass is mixed for amino 2' chloro 2 cyano 1.1 azobenzene 4 sula short time and left overnight to swell. 1 part of the fon-ic acid dimethylamide (Example 103) are suitable for monoazo dyestuff obtained according to the above example producing fast, brilliant red-orange to scarlet shades in the is dissolved in 60 parts of the same mixture of solvents mass.

by simple shaking. This solution is added :to the cellu- In the following table further monoazo dyestuflis are lose acetate solution and the whole is mixed in an open recited which may be produced in an analogous manner vessel until 60 pamts of the solvent mixture have evapas described in the foregoing examples and which are orated. The dyed mass is pumped into the spinning suitable for dyeing cellulose diacetate and triacetate fibers in the mess. They correspond to the formula /CHzCHz-OC -R7 Rs-OzS N=N -N\ ii CHrCHz-OC O-R7 R Y I) Examples R3 R4 R5 Ru R1 Y Color N(G4Hq)= 01 H 01 02115 01 Orange. N (C4H9)2 H SO:N (0411a): H NH-CaHs C1 D0.

(0113 H ON 7 H NH-GH C1 Scarlet. N (C4H9)2 H 131- H N H-CaHa O1 Orange.

4119): H 01 H NH-GQH5 01 Do. N(O4H) O6H5 H 01 H NH-C5H 01 D0. N (CqH5)CHzOHr-CN H Cl H NHCOH5 B1 D0. NHOH2CHz-CHr-OOH; H 01 H NH-CBHS C1 D0. NH-CHzOHa0-OHg-OH: 01 H 01 NEE-00H, 01 Do. NH-CaHs 01 H 01 2H5 NH-CO-CaH'; Scarlet. NH-O5H5 Cl H 01 NH-CGH5 NH-OO-C9H1v Do. N(G3H7)O H H H NHOBH5 NH--CO-C11Ha5 Do. N(CHa)z H SOPCHE OH=CHQ H NH-CsH17 O1 Orange NH-Odilg ocgH H 1 NH-Calih C1 D0. N(CH2OHrOH)g C1 C1 01 NH-Cfllih 01 Do M0 11 Br Br NH-OGEs 01 Do. N (cm H 01 H NH-C6H4-OH3 C1 D0. N(C4Ho)a H ON H NH-O5H4-OH; 01 Do. N(GH3)2 H Soy-CH5 Bl NH-C7H5 C1 D0. NH- CaHu H S0a-NH-C&H H NH-CH7 C1 D0.

Formulae of representative dyestuffs of the foregoing Having thus disclosed the invention what We claim is: examples are as follows. 1. A monoazo dyestuff having low solubility in water,

Example the formula of which is 01 O1 R l '/lower alkyl H10 1 N-so,O-N=NC -N O G CHTCHTON H30 CHTCHHW wherein R is a member selected from [the group con- Example 18: sisting of hydrogen and lower alkyl.

01 2. The m'onoazo dyestuff cor-responding to the formula GET-CH3 Cl I-IHC-HN-OHGmNGN I 0H3 CHQ-CHz-CN 4O z N=N N\ Example 22: i GHrCH CN 3. The monoazo d e-tuff corre w t CHTCHTOHrOHZ y s spondm to the formula CHz-CH:

o1 HaC-HN-O S 4N: N\ I CHrCm-CN HaCHNOzSON=NC -N Example 34:

C1 CH OH -CH -OE 4. The monoazo dyestuif cor-responding to the formula Example 47: CHa-CHz-CN CHa-CHa-OO OC a HaC HBO

References Cited in the file of this patent UNITED STATES PATENTS CHa-CHa-CN 2,891,942 Merian June 23, 1959 

1.A MONOAZO DYESTUFF HAVING LOW SOLUBILITY IN WATER, THE FORMULA OF WHICH IS 